Treatment of oxidized hydrocarbon mixtures and products thereof



Patented Jan. 8, 1952 UNITED sr-Aras Parent orsics TB IEATMENTQOFOXIDIZED HYDROCARBON MIXTURES 'ANDJPRODUCTS THEREOF Carl; ZellnemProvidence, and Fred 'Lister, ElizahethrNal, assignors to Tide WaterAssnciatedOilCompany, Bayonne, N. J., a corporation; of DelawareNo'Drawingi Application July 27, 1949;

' Serial No. 107,138

19 Claims, (Cl. 260-485) The present invention relates to a method for,treatment of certain oxidized. hydrocarbon mixtures andproductsresulting; fromisuchitreatw ment thereof.

In the oxidation of: hydrocarbonsbyliquid with a, negligiblegamountiifjy any; lot;- crystalline diiunctional substances; Oh, they otherhand,,

and) as" is described. more; fully hereinafter, by

varying the conditions. under: which the oxida tion is effected oxidizedhydrocarbon mixtures may (be: obtained} that have relatively highsaponification values; e; g at least about 406 mgs; of KOHperrgram andsubstantially higher, on a on the orderof 5001 to 625 or more, Such"oxidized hydrocarbon mixtures; contain;v illfiddition to monoiunjctionalsubstances; a substantial amount of crystalline. difimctional sub'-'stances, e; g;, dibasic acids, andsubstancesrcom vertible thereto, theattainment of" such? relatively? highi saponificationvalues beingeffectiveto: convert a substantial amount of the hydrocarbons topolyfunctionalg monoiunctional" substances. Generally speaking, such Ioxidized hydrocarbon mixtures, prepared" byliquid' phase oxidation oihydrooarbons by reaction thereofv with oxygen Off a free-oxygen;containing gas; and particularly- When the r oxidation iscontinued torelatively high saponificationva-lues, are characterized?by having anacid i value substantially lowerthan the saporiifi? cation value and, inmany instances, the acidto- J saponificationdifferential about of thesaponification' value.

often represents copending' application, Serial No: 625,961

(HOWU: Si Patent No; 2;486 ,454)", fi1ed"October 31; l 9i5'g of 'whichone of us is the inventor; a method; and products resulting therefrom,has

'been descrihed for" treatment offi hydrocarbons; in liquid phase underrcontrolled conditions? by re action of thehydrocarbons withoxygen' of afree oxygen containing gas; Al'I- important aspecti of ltheiinventiondisclosed thereine isa thatf Wheel in preference to of the conditionsdisclosed, suppression of resinification is obtained. both at the low aswell as at the higher,stages of, oxidation. Suppression ofresinification at theiearly stages of oxidation isimportantginthatittnot only enables prepara-- tion of. crudeoxidationmixtureswith minimized formation of resinous materialsatvarious stages of theoxidation but, of considerable importance, enablescontinuance of the" oxidation to relatively high saponification values,e. g., over- 400,

3 whereby oxidized hydrocarbon? mixtures-may be prepared that' containa; substantial" amount of dibasic aoidswand polyfunctionalsubstancesconvertible thereto, of the aforesaid copending. application comprisescontacting hydrocarbons; in liquid 1 phase with a gas containing freeoxygen at an oxidizing temperature while controlling the rate of "feedofthe gas to the hydrocarbons, and the gas'distribution therein tomaintain dispersed. in the:

M hydrocarbon. an amount oil gas suflioient to cause combination ofoxygen atan average rate,

related to the oxidizing temperatureas follows:

substantially above 1.5 litersof'oxygen per hour,-

per kilogram of hydrocarbons. at an oxidizing temperature of: 120" C3,,substantially, above 23 litersor" oxygen per hour per kilogramofhydrocarbons at anoxidizing temperature of C., andsubstantially above135.. liters. of oxygenper hour perkilogram of hydrocarbons at anoxidizing temperature of C;

Oxidized hydrocarbon mixtures, prepared in the manner disclosed in the"aforesaid copendr'.

in'g application are characterized" by, having a substantial diflferencebetween theacid andvthe saponification value, the components accountingfor the differential beinglargely composed.

of partially oxidized hydrocarbons, of complex chemicalstructure; Suchoxidized hydrocarbon mixtures are distinguishable over oxidizedhydrocarbon mixtures known to the art, and pre: pared by use of nitrogencompounds as oxidizing agents as, by use of such agents, more drasticoxidation occurs 1 whereby" intermediate; oxidized:

compounds are either i not formed to a; substan tial extent or; ifformed; are substantiallyv destroyed during the oxidation. Due to thepresence of the stated; partially oxidized substances of complexstructure 1 largely accounting for thediiierence between the acidandsaponification' values of oxidizedhydrocarbon mixturesprep-areddnvac'cordance with the; aforesaid ap' plication, such oxidizedhydrocarbon mixtures present problems that are not asfar as we areaware; encountered in oxidized" hydrocarbon mixtures preparedrby use ofnit'rogen compounds In oneillustration, the process as oxidizing agentsand particularly, by hydrocarbon mixtures oxidized with nitrogencompounds to the extent of preparing crude oxidized mixtures containinga substantial amount of dibasic and other polyfunctionalacids. Inillustration of certain problems encountered due to the presence of asubstantial amount of intermediately oxidized components in oxidizedmixtures prepared in accordance with the aforesaid copendingapplication, reference is made to copending applications Serial No.668,317 (now U. S. Patent No. 2,486,455), filed May 8, 1946, and 769,761(now U. S. Patent No. 2,486,456), filed August 20, 1947, of which one ofus is the inventor, disclosing thermal and catalytic treatments forcrude oxidized hydrocarbons prepared in accordance with the method ofcopending eplustration thereof, an oxidized hydrocarbon mixture,prepared by oxidizing a scale wax (105 to 108 F. melting point) in themanner disclosed in copending application Serial No. 625,961 (now U. S.Patent No. 2,486,454), and "having an acid value of 408.8 and asaponification value of 632.8, was distilled and the results obtainedare set forth in Table I. In that table, the figures of 94.9% shown asthe weight yield (based on the weight of the oxidized hydrocarboncharge) and the 68.5% shown as the weight of saponifiable constituentsrecovered in the distillate include 3.1% (by weight of charge) of anaqueous acidic solution recovered in a Dry Ice trap employed in carryingout the distillation, said acidic solution containing 3% of saponifiableequivalents based on the saponifiable equivalents in the charge.

Table I Distillate yields Total yield Fraction up to 100 C. at Fractionat loo-175 0. Fraction from 175l97 C.

. 0.2 mm. pressureat 1.0 mm. pressureat l to 3.2 mm. pres- AcidValue-=333.7; Acid Value-632.8; sure-Acid Value= Sap. Value=6l0.4 Sap.Value-W392 459.2; Sap.Value=652.4

Run Bottoms (by Weight No. gggfi gf Per Cent of Per Cent of Per Cent ofbased onCharg Per Cent by able Equiw Saponifi- Bapomfl; Sapon1fi Weightof alents m able Equlvable Equivable Equiv- Charge Re- Distinates PerCent alents Per Cen alents; Per Cent elents covered as based on byWeight (based on by Weignt (based on by Weight (based on DistillatesBatman} of Charge Saponiflof Charge Saponifi; of Charge SaponifiandBotable Emma able Equivable Equ v able'Eqniv- I toms ments in alents inalents in. alents in Charge Charge) Charge) Charge) 1 94. 9 68. 14.6 10.5 23. 3 27.6 26. 7 27. 4 26.9 Per Cent (hard, brittle mass at 280 C. and3.2 mm. pressure) plication .Serial No. 625,961 (now U. S. Patent No.2,486,454) to effect improved recovery of crystalline dibasic acids bysuppressing the effect of the intermediate oxidized hydrocarbons toinhibit recovery of crystalline polyfunctional components from the crudeoxidized mixture.

Oxidized hydrocarbon mixtures disclosed in and prepared by the methodset forth in copending application Serial No. 625,961 (now U. S. PatentNo. 2,486,454) represent the types of starting materials contemplatedfor use in the practice of this invention, as is described more fullyhereinafter. Investigations directed to the use of such oxidizedhydrocarbon mixtures for recovery of certain desirable constituentsthereof has revealed that such oxidized hydrocarbon mixtures perform inan unexpected manner. Since such oxidized hydrocarbon mixtures contain asubstantial concentration of saponifiable constituents, consisting ofboth the compounds that account for the acid value as well as compoundsthat account for the difference between the acid and saponificationvalue, it is highly desirable to treat such oxidized hydrocarbons torecover saponifiable constituents therefrom in highly useful form and ina simple and economic manner. Resort has therefore been made to use ofconventional distillation in an attempt to recover the saponifiablevalue of such oxidized hydrocarbon mixtures in distillate form but suchattempts have revealed that, by subjecting the crude oxidized mixturesto conventional distilling operations, the amount of saponifiableconstituents recoverable in the distillate or vdistillates obtainabletherefrom totals substantially less than the saponifiable value of thecrude oxidized mix- The data in the foregoing table clearly shows thatby subjecting the crude oxidized hydrocar bon mixture to distillation,94.9% of the charge (by weight) was recovered, the 94.9% recovery beingthe sum of the distillate obtained plus the bottoms product (26.8%)which was a hard, brit tle mass. Such a substantial amount of bottomsproduct was formed even though the distillation, carried out to abottoms temperature of 280 C. at 3.2 mm. pressure, was not sufficient toefiect decomposition as, during the distillation, no evidence ofsubstantial, if any, evolution of carbon dioxide was observed. However,and although the total products recovery amounted to 94.9% of thecharge, the saponifiable constituents of the charge were recovered indesired distillate form in an-amount of only 68.5% based on the saponidesirable saponifiable constituents present in such mixtures.

The present invention is directed to a method for treatment of oxidizedhydrocarbon mixtures such as those of the type disclosed and prepared inthe manner set forth in copending application Serial No. 625,961 (now U.S. Patent No. 2,486,454) to provide compositions which, as far as we areaware. are novel and which are improved-in susceptibility to treatmentby distillationfto produce improved yields, in desired distillatedorm,of saponifiable equivalents present in.- ture sub ected to thedistillation. In specific il- 79 the oxidized hydrocarbon m xture. Theimproved.

amount,- in suitable'form as distillates, of the saponifiableequivalents in the oxidized hydro carbo mixture. For example, whereas inrun No. 1, 68.5% of the saponifiable equivalents were" product, uponanalysis; showed that combination of the alcohol with saponifiablegroups of the oxidized hydrocarbon mixture had occurred to the extent of93.2% based on the acid value of recovered in the distillate obtainablefrom the the oxidized mixture. The alcohol-treated mixcrude oxidizedhydrocarbon mixture, the 91.9% ture, upon being subjected todistillation, gave recovery in run No. 2 represents a substantial andthe results set forth in following Table III.

Table III Distillate Yields Total Yield Fraction up to 100 C. atFraction. from l00175 0. Fraction from 175-235C. 0.2 mm. pressures-Acidat 0.2 mm. pressureat 0.6-1.3 mm. pres- Value=39'.2; Sap. Value AcidValue=11.2; Sap. sure-Acid Value =375.2 Va1ue=285.6 39.2; Sap.Value==29l.2

' Per Cent of 1 I g Bottoms (by Weight Per Cent by Saponificatron PerCent of Per Cent of Weight of Equivalents ggg g gg fg SaponificationSaponification based on Charge) Charge Rein Distillates Per Cent by Eulvalents Per Cent by Equivalents Per Cent by Equivalents covered asplus Bottoms Weight of on Weight of (based on Weight of (based onDistillate (based on Charge saponificaflon Charge Saponiiication ChargeSaponification .B the slajpomiiiiatign Equivalents lgquilrxalengslilqiggalengs ot oms qu va en s n arge n arge in Charge) m Charge) 92.3100.3 11.0 12.8 45.5 44.0 24.2 27.9 11.6 (liquid at 325 C. at I g 1.3mm. pressure and containing 15.6% of Saponiiication Equiv i alents basedon Saponificatiou Equivalents of Charge).

was in the form of a viscous liquid. As in run 1 No. 1, no evidence ofcarbon dioxide formation was observed with run No. 2, thus illustratingthat the highly improved results of run No. 2 were not obtained at theexpense of carrying out the distillation to the extent of effectingproduct decomposition as would be evidenced by evolution of carbondioxide. I Although the foregoing data illustrates the unexpectedimprovement in recovery of desirable constituents of the crude oxidizedhydrocarbon mixtures, such improvements having. resulted by practice ofthis invention, several other examples are set forth hereinafter showingthe flexibility-- of the present invention when practised with use ofhydroxyl-bearing organic compounds and/or reaction conditions other thanthose employed in the treatment described for preparation of the chargefor run No. 2 (Table II) A crude oxidized hydrocarbon mixture, pre paredby oxidizing a scale wax (105 to 108 F. melting point) in the mannerdisclosed in copending application Serial No. 625,961 (now U. S. PatentNo. 2,486,454) and having an acid value of 341.6 and a saponificationvalue of 548.8 was mixed with an amount of 2-ethylhexanol double thetheoretical equivalent based on the saponification value of the oxidizedhydrocarbon mixture., The alcohol-containing mixture was reiiuxed for 5hours at the boiling temperature of 2-ethylhexanol with periodicwithdrawal of waterv formed during the reaction. The alcohol-treatedbased on the saponification value of the oxidized A crude oxidizedhydrocarbon mixture, as used in run No. 1 (Table I), was mixed withbutanol in an amount substantially double the theoretical.

tion of the alcohol with saponifiable groups of the oxidized hydrocarbonmixture had occurred to the extent of 39% based on the acid value of theoxidized mixture. The reaction product, upon being subjected todistillation, gave the results set forth in following Table IV.Comparison of the data in Table IV with that of Table I clearlyevidences that the butanol reacted product, in which butanol combinationwas effected to the extent of 39% based on the acid value of theoxidized hydrocarbon mixture, provided a highly improved yield ofsaponifiable equivalents in the distillates recoverable therefrom.

A crude oxidized hydrocarbon mixture,ias used in run No. 1 (Table I),was mixed with an amount of methanol double the theoretical equivalentweight of charge) of an acidic aqueous solution recovered in a dry icetrap employed in carrying out the distillation, said acidic solutioncontaining 3.4%v of the saponifiable equivalents of the, charge. Hereagain, upon comparison of the data The alcoholnew if; Table IVDlstillate Ylelcls Erection ammo-175 :0. Lot 1 mm pressureTAcidifiiggluwim; Sep -Valueiercent Bottoms (by A e of 1:WeightbasednuCharge) Pet a 'Sapomfiable Percent of BerQent ofWEqnivalents .15: Saponlfiable aponlfiable y in Distillates or CentEquivalents 2 plusBottoms byWeight "(Basedpow yWelght .:.(based on,aoLCh fi Charge v ,Sapotfl fiable Equivalents inQharge) :;;:1;8 7.1 41.4214 20.70 18.1 (vlscous mass congtainingl klz; oisaponif1ableequivalents F 1 based on saponifiable equivalents in charge) ineTableVlwith TableI, the alcohol-treatedt-mixture provided. a highly improvedyieldrofxsaponlliable. iequivalents in. distillateaform.

jequivalent to all or substantially all of the acid value; ofthe.oxidized hydrocarbon mixture.

Thegdlstillates obtained by distillation of. the

Table V Distillatdyields Total yield Fraction up to 1002C}. ateEl80fi01l front-100th I70 -Fractloniroml70 to240' O.

t at 0.1 mni..'pressure n at0:1-51dmmxpressurdi Acid-Value==44.6; Sap.-Acicl YalueylQSmSap. Value=628 i "--Va1ue-575 v. Per. Cent Bottoms (byI?% 3e%1 t b y Weightbased or Oharge 1 0 tb s n "1 Cantor PerCentof fiSaponiilable saponjfiable .T i Fig-$22 6 2: Percent by ,Equivalents: PerCent by Per. Cent b Equivalents f' 3 i vWeight of v,,(bascd on ltfelghtof l -Welght of" -(based on $5 on Qharge, Sapo'nifiable Charge n 5 3 5 1lol im tat s Sapt mifiable Equivalents Eq alents .Equivalents gharge)Charge) iii-Charge) i i 93.2 a 85.0 24.8 2e. 5 22.9 w 28.9 28:5 12.6(semi-liquid at 350 i i O. at 5.5 rnm pressure and containing 3.4 PerCent of saponifiable equivalents of; charge).

'nstisappa ent from th ore o n thehlshhr a 1 improved; results embodied,herein are; obtainable by effecting combination of at least ,a: portion,

i asvcalculated onthe, said ,value, of the saponifiable groups intheoxidized hydrocarbon mixture w-ith-the hydroxyl-bearing compound.,. .Asis fur- .wthenapparentd-rom the foregoing, .theamount of -,saponifiablegroups combined may be;varied,-.;.over rather: wide; mits and yetimprovevthe asusceptibilitylicfz the, oxidized hydrocarbon mixture.ttotdistillation with-improved recovery of sapo ifiableequivalentsvthereof in desirable; distillate;;1form.

As-lshown by the foregoing dataynillust ifiting y specific; embodimentsof the invention, a-jmarked improvement. was provided by efieotingalcohol combination; with saponifiablc groups; varying from 39 to 93.2%based onthe acidvalu oflthe oxidizedhydrocarbon mixture. Althoughreflectingt combinations between the saponifiablesgroups and thehydroxyl-bearing compound .tosuch extents illustrate suitable aspects ofthe invention, theii-nvention" is not limitedthereto:as;improved 7results with: respect to recoverability of; saponifiableyequivalents maybe obtained bynefi qliing .isuch combination to lower: va1ues,.e. g.,toathe 76Xt811t ofgabo ut 20% based on the acid value of the oxidized:hydrocarbon mixturen; and to higher valuesethan set forth inztheforegoin examples, a e-"e co in sano fiahl roups-at i amext t crudeoxidized hydrocarbon mixturestreated in is accordance with thisinventionare-highly desir- -;able--produetsthatare suitable for many andvariouspurposes; Inparticular, distillates thus btained, and asillustrated-bythe distillate fracon's set-forth'jin theforegoingtables,are highly useful as organic solvents, asintermediates for-----preparation ofchemical derivatives of the con- *stituentsofthe-distillatespand areadaptable for treatmennfor -recovery from such*distillates of i chemical compounds-such as useful acids, includingpolyfunctional acidsand suchacidsin com- "bination 'with analcoholorother hydroxylbear- -ingcompounds as embo'died for use herein, and

the like. n iAlthough theexaot reasons underlying the improved resultsobtained by'practioingthis inventionsare notieknownuidue tothe chemicalcomplexitysof; compoundsspresent in the oxidized bydrocarbonrrmixtureands particularly the it commounds-accounting:forttheidifferencezbetween the acid; and, saponiiicationcvalue= thereof, it isap- 70 parent from the data presented herein that improvements in theyield of saponifiable equiva- -,lents may be obtained bysubjectingicrude oxi- ,dized -hydrocarbonmixtures, as embodiedhereginyto treatment as afore describe d. Although it is ,not intendedthat the present invention be: bound by anyttheories as; to the reasonsfor .obtaimnent of such improved results, it is possible that by wherebythe hydroxyl-bearing compound reacts" with saponifiable groups intheoxidized hydro-- carbon mixture in an amount equivalentto all or asubstantial portion of the acid value, certain components in theoxidized hydrocarbon mixtures are suppressed as to their inhibitingeffect on'the recovery of saponifiable equivalents in the form ofdistillates. That a treatment as embodied herein providessuch improvedresults is clearly unexpected. For instance, the crude oxidizedhydrocarbon mixtures embodied for use as starting materials comprise asubstantial amount of acids and, generally speaking, it is known tothose skilled in the art that acids are relatively heat stablesubstances. In view of such knowledge, and the data presented in TableI, it would appear that the difliculty encountered in endeavors toobtain high yields of recoverable saponificaton and saponificationvalues and having been prepared by contacting hydrocarbons in liquidphase at an oxidizing temperature with a gas containing free oxygen tocombine oxygen with the hydrocarbons at an average rate'related to theoxidizing temperature as follows: substantially above 1.5 liters ofoxygen per hour per kilogram of hydrocarbons at an oxidizing temperatureof 120 C., substantially above 23 liters of oxygenper hour per kilogramof hydrocarbons at an oxidizing temperature of 160 C., and substantiallyabove 135 liters of oxygen per constituents in the form of distillatesfrom the crude oxidized hydrocarbon mixture per se may be attributed to'the presence in the oxidized hydrocarbon mixtures of the complexpartially oxidized intermediates accounting for the difference betweenthe acid and saponification value of the oxidized mixture. Hence, bypracticing the present invention, whereby the oxidized hydrocarbonmixture is treated with a hydroxyl-bearing compound as aforedefined toefiect combination in an amount equivalent to all or a substantialportion of the acid value, thereby providing compositions whichapparently still contain a substantial amount,'or all, of the portionaccounting for the difference between the acid and saponification valuein uncombined form, it is clearly unexpected that the treated mixtures,which still contain the components that are believed to inhibit recoveryof saponifiable constituents, would be susceptible to treatment bydistillation with improved recoveries as aioredescribed. Although, in.

treating crude oxidized hydrocarbons as aforedescribed, a reactionoccurs whereby combination of the hydroxyl-bearing compound is efiectedwith a certain amount of the saponifiable groups in I the crude oxidizedmixture, it appears that, in addition thereto, such a treatment in somemanner alters the molecular structure of certain components present inthe portion accounting for the difference between the acid andsaponification value of the oxidized hydrocarbon mixture. It is believedthat by use of such a treatment, certain normally non-distillablecomponents of the oxidized hydrocarbon mixture are altered in molecularstructure, possibly by depolymerization, or are inhibited againstpolymerization, whereupon such normally non-distillable compounds arerecoverable by distillation to provide substantially increasedrecoveries of saponifiable equivalents from the oxidized hydrocarbonmixtures.

Although the present invention has been described in conjunction withcertain preferred embodiments thereof, those skilled in the art. willreadily recognize that variations and modifications can be made. Suchmodifications and variations are to be considered to be Within thepurview of the specification and scope of the appended claims.

We claim: v

1. A method for treating an oxidized hydrocarbon mixture, as definedhereinafter, to increase the recoverability of saponifiable constithourper kilogram of hydrocarbons at an oxidizing temperature of 180 0.,which comprises reacting said oxidized hydrocarbon mixture with anorganic compound containing a hydroxyl group possessing alcoholiccharacteristics to combine saponifiable groups of said oxidizedhydrocarbon mixture with said hydroxylbearing compound and recover fromsaid reaction mixture an amount of alcohol reacted products not inexcess of the amount of alcohol reactables in said oxidized mixture ascalculated on its acid value.

2. As a new composition, a reaction product prepared by the method ofclaim 1.

3. As a new composition, a distillate fraction obtained by distillationof the reaction product defined in claim 2.

4. A method, as defined in claim 1, wherein the hydroxyl-bearingcompound is an aliphatic alcohol.

5. As a new composition, the alcohol reaction product prepared by themethod of claim 4.

6. A method, as defined in claim 1, wherein the oxidized hydrocarbonmixture has a saponification value of at least 400 mgs. of KOH per gram.

'7. As a new composition, the reaction product prepared by the method ofclaim 6.

8. A method, as defined in claim 1, wherein the reaction product issubjected to distillation for recovery of said alcohol reacted products.

9. A method, as defined in claim 1, wherein the oxidized hydrocarbonmixture is combined with said hydroxyl-bearing compound in an amountequivalent to at least as calculated compound is a monohydric alcohol.

; 12. A method for treating an oxidized hydrocarbon mixture as definedhereinafter to increase the recoverability of saponifiable constituentsthereof in distillate form, said oxidized hydrocarbon mixture beingcharacterized by having uents thereof in distillate form, said oxidized,

hydrocarbon mixture being characterized" by a substantial differencebetween acid and saponification value and having been prepared by liquidphase rapid oxidation of hydrocarbons with a gas containing free oxygen,which comprises reacting said oxidized hydrocarbon mixture with anorganic compound containing a hydroxyl group possessing alcoholiccharacteristics to combine saponifiable groups of said oxidiedhydrocarbon mixture with said hydroxyl-bearing compound and recover fromsaid reaction mixture an amount of alcohol reacted products not inexcess of the amount of alcohol reactables in said -Z-o'xidized mixtureas calculatedon its acid value.

13. A method, as defined in claim 12, wherein the oxidized hydrocarbonmixture has a saponification value of at least 400 and has been preparedby oxidation of a predominantly parafiinic hydrocarbon mixture.

14. A method, as defined in claim 13, wherein the hydroxyl-bearingcompound is a monohydric alcohol.

15. A method, as defined in claim 1, wherein the oxidized hydrocarbonmixture has a saponification value of at least 400 and has been preparedby oxidation of a predominantly paraflinic hydrocarbon mixture, thehydroxyl-containing compound is a mono-hydric aliphatic alcohol and theoxidized hydrocarbon mixture is reacted with the alcohol at an elevatedtemperature but below the decomposition temperature of said oxidizedmixture with withdrawal of water formed during said reaction.

16. A method, as defined in claim 12, wherein the oxidized hydrocarbonmixture has a saponification value of at least 400 and has been preparedby oxidation of a predominantly paraflinic hydrocarbon mixture, thehydroxyl-containing compound is a mono-hydric aliphatic alcohol, and theoxidized hydrocarbon is reacted with the alcohol at an elevatedtemperature but below the decomposition temperature of said oxidizedmixture.

17. A method for treating an oxidized hydrocarbon mixture, as definedhereinafter, to increase the recoverability of saponifiable constituentsthereof in distillate form, said oxidized hydrocarbon mixture beingcharacterized by having a substantial difference between acid andsaponification value and having been prepared by liquid phase rapidoxidation of hydrocarbons with a gas containing free oxygen, whichcomprises reacting said oxidized hydrocarbon mixture with an organiccompound containing a hydroxyl group possessing alcoholiccharacteristics to combine a substantial portion of the saponifiablegroups in said mixture with said alcoholic compound, the

amount of saponifiable groups thus combined being not in excess of thatequivalent to saponifia'ble groups in said oxidized mixture ascalculated on its acid value, and produce a reaction mixture distillableto yield in distillate form an amount of saponifiable constituents inexcess of those as calculated on the acid value of said oxidized mixtureand substantially in excess of the amount of saponifiable constituentsrecoverable in distillate form by distillation of said oxidized mixturein the absence of the aforesaid reaction with an alcoholic compound.

18. A method, as defined in claim 1"], wherein the oxidized hydrocarbonmixture has been prepared by combining oxygen with a predominantlyaliphatic hydrocarbon mixture at an average rate related to theoxidation temperature as follows: substantially above 1.5 liters ofoxygen per hour per kilogram of hydrocarbons at an oxidizing temperatureof C., substantially above 23 liters of oxygen per hour per kilogram ofhydrocarbons at an oxidizing temperature of 0., and substantially above135 liters of oxygen per hour per kilogram of hydrocarbons at anoxidizing temperature of C.

19. A method, as defined in claim 1'7, wherein the oxidized hydrocarbonhas a saponification value of at least 400 and has been prepared byoxidation of a predominantly aliphatic hydrocarbon mixture, and thealcoholic compound is a monohydric aliphatic alcohol.

CARL N. ZELLNER. FRED LISTER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,848,724 Jaeger Mar. 8, 19322,054,979 Jahrstorfer et a1. Sept. 22, 1936

1. A METHOD FOR TREATING AN OXIDIZED HYDROCARBON MIXTURE, AS DEFINEDHEREINAFTER, TO INCREASE THE RECOVERABILITY OF SAPONIFIABLE CONSTITUENTSTHEREOF IN DISTILLATE FORM, SAID OXIDIZED HYDROCARBON MIXTURE BEINGCHARACTERIZED BY HAVING A SUBSTANTIAL DIFFERENCE BETWEEN THE ACID ANDSAPONIFICATION VALUES AND HAVING BEEN PREPARED BY CONTACTINGHYDROCARBONS IN LIQUID PHASE AT AN OXIDIZING TEMPERATURE WITH A GASCONTAINING FREE OXYGEN TO COMBINE OXYGEN WITH THE HYDRCARBONS AT ANAVERAGE RATE RELATED TO THE OXIDIZING TEMPERATURE AS FOLLOWS:SUBSTANTIALLY ABOVE 1.5 LITERS OIF OXYGEN PER HOUR PER KILOGRAM OFHYDROCARBONS AT AN OXIDIZING TEMPERATURE OF 120 C., SUBSTANTIALLY ABOVE23 LITERS OF OXYGEN PER HOUR PER KILOGRAM OF HYDROCARBONS AT ANOXIDIZING TEMPERATURE OF 160 C., AND SUBSTANTIALLY ABOVE 135 LITERS OFOXYGEN PER HOUR PER KILOGRAM OF HYDROCARBONS AT AN OXIDIZING TEMPERATUREOF 180* C., WHICH COMPRISES REACTING SAID OXIDIZED HYDROCARBON MIXTUREWITH AN ORGANIC COMPOUND CONTAINING A HYDROXYL GROUP POSSESSING ALCOHOLCHARACTERISTICS TO COMBINE SAPONIFIABLE GROUPS OF SAID OXIDIZEDHYDROCARBON MIXTURE WITH SAID HYDROXYLBEARING COMPOUND AND RECOVER FROMSAID REACTION MIXTURE AN AMOUNT OF ALCOHOL REACTED PRODUCTS NOT INEXCESS OF THE AMOUNT OF ALCOHOL REACTABLES IN SAID OXIDIZED MIXTURE ASCALCULATED ON ITS ACID VALUE